Heavy metal salts of alkyl phenol sulfides and method of making same



Patented Jan. 10, 1950 SULFIDE S AND SAME METHOD OF MAKING John G. McNab, Cranford; N. J'., and Walter T.-

Watkins, Jr, Norfolk, Va., assignors to Standard Oil Development Company, a. corporation of Delaware No Drawing. Original application December 30,

1939, Serial No. 311,838.

Divided and this application October 18, 1944, Serial No. 559,258

15 Claims. (Cl. 260-439) This invention relates to a novel type of metal M compounds and methods of preparing same.

This is a division of our copending application Serial No. 311,838, filed December 30, 1939, now issued as Patent Number 2,362,293, granted November '7, 1944.

This invention relates to a, class of metal compounds of which the cobalt salt of tertiary amyl phenol thioether is representative. This compound, which might also be called a cobalt tertiary amyl phenol sulfide, or a sulfide of cobalt tertiary amyl phenolate, is believed to have the formula:

[CO(C5H11YCBH3YO) 2511 where n is one or more. If the various groups attached to the aromatic nucleus are so positioned that the amyl group. is in an. ortho position to the oxygen, and the sulfur. linkage is in a meta position to the oxygen, this compound probably has the following graphic formula in its simplest form:

Obviously, with both the cobalt and the phenol divalent, quite large complexes can theoretically be built up. It should be understood that the position of the various substituents around the aromatic nucleus may be varied without depart ing from the scope of the invention,

A similar disulfide compound may be used in .Which the group S- in the above graphic formula is replaced by the-group or if preferred by the group '-S-S, or even higher polysuliides may be used.

These various compounds can be produced by preparing the corresponding alkyl phenol sulfides or disulfides, which per se are known, and converting these into the corresponding sodium or potassium salts thereof, 'as by treatment with sodium or potassium hydroxidaand then converting the resultant derivative of the alkali metal into the corresponding derivative of cobalt by any suitable means, such as by double decomposition with a suitable corresponding cobalt compound, such as the chloride, nitrate, etc.

The invention may be described morebroadly -as comprising a product having an alkyl, sub! stituted aryl metal oxide in which the oxygen of the metal oxide group is directly attached to the aryl nucleus in which at least two alkylated aryl nuclei-are interconnected by at least one atom of an element of the sulfur family, in which the 7 metal is a metal of group VIII, series 4, of the Mendeleeff periodic table, and in which the alkyl radicals each contain at least 4 carbon atoms.

The aryl nuclei may have attached other substituents for the hydrogen atoms and such substituents may be organic, inorganic, or both, for example, alkyl radicalsandgroups containing one or more of the non-metallic, elements belonging to groups V, VI, and VII of the periodic system Mendeleefl) nitrogen, phosphorus, oxygen, sul-, fur, and halogensxas in amino, nitro, phosphite, phosphate, hydroxy, alkoxy, sulfide, thioether, mercapto, chloro groupings, and the like. Somewhat more specifically, the cobalt, nickel or iron derivatives may be used of the following type of phenolic compounds:

The configurations of the compounds are not limited to those shown in the illustrated structures, for the substituents may be in ortho, para, or meta relations to oneanoth'er. Also, the substituents in any aromatic nucleus may be alike 'or different.

The aromatic nucleus may be polycyclic as in naphthalene, phenanthrene, diphenyl, etc. Where oxygen occurs, it may be replaced by sulfur, selenium or tellu'rium.

In the case where the metal is trivalent such as ferric iron, one, two, or all three of the valences of the ma be connectedv to a phenolic oxygen. For instance, in case of a trivalent metal the thioethers of alkyl phenolate may have a formula such as the following:

As these substituted phenolates are generally a made by reacting the corresponding phenols with a metal oxide or hydroxide (either the onedesired, or the sodium or potassium compound to' be converted into the one desired), the amount of metal in the phenolate product will depend on the proportions of reactant used, and if prod-- ucts having different proportions are possible,-

the products will usually consist of a mixture,

which may be used as such or may be separated into several constituents. For instance, as will be seen from the experimental data given later; nickel derivatives of tertiary] amyl phenol thioethers have been prepared which contain 3 different proportions of nickel. It is probable that, the normal compound containing 1 nickel atom per thioether molecule, which should contain 18% NiO, should have the followingfl graphic formula:

On the other hand, if only enough metal is reacted with the phenolic compound to combine with one of the hydroxyl groups it is likely that the resultant product will have the following graphic formula:

I on 0 OH CsHu H CHu 06H sv s where M is a metal selected from the group consisting of cobalt, nickel and iron, R represents one or more alkyl groups having enough carbon atoms (preferably a total of at least to insure solubility of the total compounds in mineral oil, Ar is an aromatic nucleus, preferably a benzene nucleus, a: is l or 2, and n is the valency of the metal. More particularly, compounds having the following general formula are preferred:

1 mctnanosnao) is where M is cobalt, nickel or iron, n is at least 4, and preferably 5 .or more, and where the group CnH2n+1 is preferably a branched chain alkyl group.

secondary and tertiary types, because alkylatiorl of a simple phenol occurs more readily with Commonly, the

branched aliphatic reactants. alkylation reaction involves a condensation of olefins with the simple phenols, the reaction being catalyzed by anhydrous metal halides, sulfuric acid, phosphoric acid, or certain activated clays.

As olefinic reactants, refinery gases containing propylene, butylenes, amylenes, etc., are economically useful, although individual olefins,

--e. g., isobutylene, iso-amylene, diisobutylene, triphase reaction at relatively low temperatures is preferred; with phosphoric acid the reaction For the objects stated, the metal phenolates .have been preferably prepared from phenolic compounds readily obtainable by-alkylation of the simple phenols or by extraction from high 'the'desired phenol sulfides are principally of the maybe carried out in the vapor phase.

'As starting materials for conversion into the metal phenol sulfides, the phenols may contain one or more substituents which provide a desired number of saturated carbon atoms in groups having the form of straight chains, branched chains, or even rings. Monoalkyl or polyalkyl phenols aresynthesized conveniently by alkylating a phenol with branched chain olefin polymers, such as diisobutylene, di-tert-amylene, or other suitable agents, such as alcohols, alkyl sulfates, alkyl phosphates, or alkyl halides, thereby forming carbon-to-carbon bonds between the aromatic nuclei and the alkyl groups.

Petroleum phenols which qualify for the present purpose are considered to contain polymethylene or cycloalkyl side chains, as evidenced by their hydrogen and carbon analysis. The petroleum phenols are obtained by extraction of various stocks; chiefly from cracking process heating oil stocks, with caustic soda, and acidification of the alkaline extract with a weak mineral acid, followed'by a non-destructive distillation if desired.

By using the described methods or any other well known method for preparing alkyl phenols, the following alkylate'd phenols may be procured for preparing the phenol sulfides, e. g., tert-amyl phenol, iso-hexyl phenol, tert-octyl phenol, ditert-butyl phenol, di-tert-amyl phenol, di-normal amyl phenol, etc.

Inorganic'substituents are introduced into alkyl phenols by well known methods. For example, an alkyl phenol, e. g., tert-amyl phenol, is reacted with sulfur mono-chloride, SzClz, in about 11 /2 mole ratio and preferably in a solvent such as di-'- chlor-ethane, to produce the alkyl phenol disulfide. Using substantially the same procedure but substituting sulfur dichloride, SClz, for the monochloride, the alkyl phenols are given a thioether linkage substituent. Alkyl chlorphenols are obtained by chlorination, preferably controlled to replace nuclear hydrogen by a chloro group. This may be accomplished by chlorinating the phenol before alkylation. In such a manner, for example, 2-chlor-4-tert-amyl phenol can be produced. Nitro substituents are introduced readily into the aromatic nucleus by direct nitration, and nitro substituents can be reduced to amino groups. It is to be understood, however, that the preparation of substituted phenolic compounds which have been described does not form part of this invention and that any of the well known methods for their production may be used.

, The following experimental data illustrate the preparation of some cobalt and nickel derivatives for the substituted phenolic compounds according to thisinvention.- r 1 Example 1.-C0balt salt of tertiary amyl phenol sulfide.

7.7 grams /3 mole) of sodium were dissolvedin 150 cos. of absolute ethyl alcohol. grams /6 mole) of tertiary amyl phenol sulfide, dissolved in 100 cos. of absolute ethyl alcohol, were added. 23 grams (21.7 equals /6 mole) of cobalt chloride, CoClz (anhydrous) were dissolved in 250 cos. of

absolute ethyl alcohol and added to the above mixture with agitation. The solution turned brown. The alcohol was stripped off and the brown residue was agitated with 54 naphtha, in which the cobalt salt of tertiary amyl phenol sulfide dissolved very readily, the sodium chloride resulting from the double decomposition remaining insoluble. The solution was filtered free of sodium chloride and then distilled to strip off the naphtha. grams of a dark chocolate colored product were obtained. This product, which was cobalt tertiary amyl phenol sulfide, dissolved readily in a naphthenic base lubricating oil having a Saybolt viscosity of about 55 seconds at'210" -F., such as is suitable for use as a crankcase lubricant for Diesel engines. Analysis indicated that this cobalt salt contained 17.65% of C0304 (theoretical 19.36).

v Ea'amp'le 2.Nzckel salt of tertiary amyl phenol sulfide Some tertiary amyl phenol sulfide was converted into the corresponding sodium salt by treating with a solution of sodium in absolute ethyl alcohol, using mole of sodium and mole of the tertiary amyl phenol sulfide. 21.6 grams mole) of nickel chloride, NiClz, were suspended in 200 cos. of absolute alcohol, and the resulting suspension was added to the alcohol solution of the sodium tertiary amyl phenol sulfide.

gradually turned a dark green color. After refluxing for 24hours more thesolution was filtered free from insoluble materials (mostly sodium chloride and some unreacted nickel chloride) and the I alcohol was stripped off the filtrate yielding 67 grams of a green solid which was readily soluble in the naphthenic oil base stock referred to in Example 1. Analysis of the product indicated a content of 6.40% of nickel oxide expressed as NiO.

Based on the formula Ni(C5H11-C 6H3O) 28 the reaction do not go to completion because the calculated content of NiO should be 18.0%.

This experiment was repeated using absolute methyl alcohol instead of ethyl alcohol as the solvent for the nickel chloride, a better reaction took place, and this time a green solid product was obtained which was found to have a content of 21.6% nickel oxide (NiO), Which is slightly above the theoretical amount calculated for the formula given above. This product is also soluble in the naphthenic oil referred to.

In another experiment using methyl alcohol, 60 grams /6 mole) of tertiary amyl phenol sulfide were dissolved in 100 ccs. of absolute methyl alcohol and added to a solution of 7.7 grams A; gram-atom) of sodium dissolved in 150 cos. of methyl alcohol. 28 grams (21.6 grams equal mole) of anhydrous nickel chloride (NiC12) were .dissolved in 300 cos. of absolute methyl alcohol by refluxing, and after cooling this solution wasadded to the alcohol solution of sodium tertiary amyl phenol sulfide prepared first. A precipitate formed and another 60 cc. of alcohol were added A light solvent naphtha having a. boiling range of lilo-240 F.

The mixture was refluxed for 4 hours and.

of nickel chloride (NiCl2) tion.

and the mixture was permitted to stand over night. After recovering the precipitate, dissolving it in 54 naphtha, filtering off the residual sodium chloride and evaporation of the naphtha, a yellow-colored product was obtained which had a nickel oxide content of 17.9% NiO, which corresponds closely with the theoretical 18.0% for the compounds having the formula v V Ni (C5H11CsI-I3O) 2S This product is also soluble in the naphthenic oil referred to.

Example 3.Nz'clcel methoxo salt of tertiary amyl phenol sulfide 15.5 grams gram-atom) of sodium were dissolved in 300 cc. of absolute methyl alcohol. .60 grams /6 mole) of tertiary amyl phenol sulfide dissolved .in cc. of methyl alcohol were added. ,44 grams (23.2 grams equal mole) of anhydrous nickel chloride (NiCla) were dissolved in 400 cc. of trimethyl alcohol by refluxing. The nickel chloride solution was added to the above with agitation. A precipitate formed, and after standing for several hours the solution was filtered off, the precipitate being air-dried and Example 4.'Niclcel salt of tertiary amyl phenol disulfide 7.7 grams /3 gram-atom) of sodium were dissolved in cc. of pure methyl alcohol. 65 grams /6 mole) of tertiary amyl phenol disulfide (obtained by treating tertiary amyl phenol with sulfur monochloride (S2Cl2 dissolved in 100 cc. of methyl alcohol, were added to the first solution to form the sodium salt of tertiary amyl phenol disulfide. 25 grams (21.6 grams equal /6 mole) were dissolved in methyl alcohol by refluxing and the resulting ,solution was slowly added to the solution of sodium tertiary amyl phenol disulfide with agita- After standing, the precipitate which formed was filtered ofi and dried. The yield equalled 68 grams.

The filtrate was stripped free of alcohol, leaving a residue of 39 grams. These two residues were combined and refluxed with 54 naphtha for .a few minutes, cooled, settled for a day and the supernatant liquid was drawn 01f and stripped -.free of naphtha, leaving a residue of 75 grams of greenish-yellow solid which dissolved readily in the naphthenic oil referred to in Example 1 on heating. This product contained 15.49% of nickel oxide (N10), which corresponds fairly well with the theoretical 16.72% calculated for the formula Ni(C5H11C6H3-O) see, the nickel salt of tertiary amyl phenol disulfide.

Example 5.-Cobalt salt of tertiary amyl phenol sulfide This is the laboratory method of preparation which was subsequently adopted for the commeri m u c u e of c tte r m lip sn l sulfide.

. 71.6 grams of tertiary amyl phenol sulfide-were about 150 F. and agitateduntil the caustic soda 7 was completely reacted to give a yellowish-brown solution of sodium tertiary amyl phenol sulfide in the alcohol. A solution of 2'7 .6 grams of cobalt chloride hexahydrate in 150 cc. of isopropyl alcohol, prepared by warming the alcohol to about 125 F. and stirring, was then added, with stirring,

'to the alcoholic sodium tertiary amyl phenol sulfide solution, producing a brownish paste of cobalt tertiary amyl phenol sulfide suspended in alcohol.

320 grams of a Coastal naphthenic lubricating oil base stock having a viscosity of about 55 seconds Saybolt at 210 F. (a sufiicient quantity to give a 20% solution of the cobalt salt) was then added and the alcohol was removed by stripping in vacuum. In order to assist in re moving the last portion of the solvent, the product was blown with air. The finished product was filtered through paper and the filtered 20% concentrate of cobalt tertiary amyl phenol sulfide in the naphthenic lubricating oil base stock was found upon analysis to contain 3.42% of cobalt oxide (C0304) (which checks satisfactorily with the theoretical amount of 3.33%).

Corresponding cobalt, nickel or iron salt's'o'f other alkyl phenol sulfides may be prepared, for instance, by substituting polysulfide or polymers, such as the dimers, trimer's, and tetramers of the alkyl phenol thio-ethers used in" the above examples. Also, the corresponding metal salts of the corresponding selenides and tellurides may be prepared, although the sulfur compounds are preferred.

The various products obtained may be purified, if desired, by fractional crystallization, ex-

traction, precipitation with selective solvents, etc. Also, impurities may be removed by treatment with suitable adsorptive agents such as clay.

oils, in which they are particularly effective in {inhibiting oxidation and the formation of sludge under the high temperature conditions of service in internal combustion engines.

This invention is not to be limited to any of the specific examples presented herein, which were sisting of an alkyl substituted aryl metal oxide in 'which the oxygen of the metal oxide group is directly attached to the aryl nucleus, in which at least two alkylated aryl nuclei are interconnected by at least one atom of an element of the sulfur family in which said metal is a metal of group VIII, series 4, of the Mendeleeff Periodic Table, all .of the valences of said metal being satisfied by an aryl oxide group as defined above, and in which the alkyl radicals each contain at leas four carbon atoms.

2. Compound according to claim 1 in which said metal is cobalt.

3. Compound according to claim 1 in which said metal is nickel.

4. A metal salt of an alkyl phenol sulfide where- The new compounds of the present invention..

are useful as additives for mineral lubricating in the metal is a metal of group VIII, series 4, of the Mendeleefi Periodic Table, all of the valences of the metal being satisfied by an alkyl phenol sulfide radical, and wherein each of the alkyl radicals contains at least four carbon atoms.

5. A neutral cobalt salt of an alkyl phenol sulfide in which each alkyl group contains at least 4 carbon atoms.

6. A neutral nickel salt of an alkyl phenol sulfide in which each alkyl group contains at least 4 carbon atoms.

, 7. A metal salt of a tertiary amyl phenol sulfide wherein the metal is a metal of group VIlI, series 4, of the Mendeleefi Periodic Table, all of the valences of said metal being satisfied by a tertiary amyl phenol sulfide radical, and wherein each of the alkyl radicals contains at least four carbon atoms.

8. A neutral cobalt salt of a tertiary amyl phenol sulfide.

9. A neutral nickel salt of a tertiary amyl 10. A metal salt of an oil-soluble alkyl substituted phenol sulfide, each aliphatic radical containing at least four aliphatic carbon atoms, the metal being of group VIII, series 4, of the Mendeleeff Periodic Table, all of the valences of said metal being satisfied by an alkyl phenol sulfide radical.

11. The method of preparing a cobalt salt of an alkyl phenol sulfide which comprises reacting an alkali metal salt of an alkyl phenol sulfide with a cobalt halide.

- cobalt chloride.

14. A method of preparing a nickel salt of an alkyl phenol sulfide which comprises reacting an alkali metal salt of an alkyl phenol sulfide with a" nickel halide.

15. A method of preparing a nickel salt of ditert.-'amyl phenol sulfide which comprises reacting the sodium salt of 'di-tert-amyl phenol sulfide with nickel chloride.

JOHN G.'MoNAB.. WALTER T. WATKINS, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,125,961 Shoemaker Aug. 9, 1938 2,139,321 Mikeska Dec. 6, 1938 2,207,719 Cohen et al July 16, 1949 2,229,528 Shoemaker Jan. 21, 1941 2,310,449 Lightbown et al Feb. 9, 1943 2,362,289 Mikeska Nov. '7, 1944 2,366,874 Reiff Jan. 9, 1945 FOREIGN PATENTS Number Country Date 365,534 Great Britain Jan. 15, 1932 370,458 Great Britain Apr. 8, 1932 40,616 France July 27, 1932 (Addition to No. 704,635)

OTHER. REFERENCES 'Tassinari, ,Gazetta Chimica Italiana, vol. 17. 

1. AN OIL MISCIBLE CONDENSATION PRODUCT CONSISTING OF AN ALKYL SUBSTITUTED ARYL METAL OXIDE IN WHICH THE OXYGEN OF THE METAL OXIDE GROUP IS DIRECTLY ATTACHED TO THE ARYL NUCLEUS, IN WHICH AT LEAST TWO ALKYLATED ARYL NUCLEI ARE INTERCONNECTED BY AT LEAST ONE ATOM OF AN ELEMENT OF THE SULFUR FAMILY IN WHICH SAID METAL IS A METAL OF GROUP VIII, SERIES 4, OF THE MENDELEEFF PERIODIC TABLE, ALL OF THE VALENCES OF SAID METAL BEING SATISFIED BY AN ARYL OXIDE GROUP AS DEFINED ABOVE, AND IN WHICH THE ALKYL RADICALS EACH CONTAIN AT LEAST FOUR CARBON ATOMS. 